Compositions comprising sulfur-containing derivatives of hydroxyphenylbenzotriazole and process therefor

ABSTRACT

A composition that, when present in a polymer matrix, reduces the deleterious effect of UV light absorption by the polymer is provided, which comprises a sulfur-containing derivative of hydroxyphenylbenzotriazole having the formula of: ##STR1## wherein each X is selected from the group consisting of hydrogen, halogens, cyano, alkyl, phenyl group, biphenyl group, arylthio, amine, ketone, aldehyde, alkoxy, hydroxy, carboxylic acid group, oligomer and combinations thereof and can have carbon atoms up to about 20; n is a whole number from 1 to 5; n&#39; is a whole number from 0 to 4; n&#34; is a whole number from 1 to 2 and each n&#34; can be the same or different; q is an integer from 1 to 10; each Y is selected from the group consisting of --S(O)(O)--, --S(O)--, and --S--; each R can be selected from the group consisting of hydrogen, alkyl group, alkenyl group, aralkyl group, alkaryl group, and combinations thereof and can have 0 to about 10 carbon atoms; each OH group can be at either the 2&#39;- or the 6&#39;-position, or both.

FIELD OF THE INVENTION

The present invention relates to a composition comprising asulfur-containing derivative of hydroxyphenylbenzotriazole, a processfor synthesizing the derivative, a composition comprising a polymerchemically bonded to the derivative, and a process for synthesizing thepolymer chemically bonded to the derivative.

BACKGROUND OF THE INVENTION

Engineering plastics such as poly(arylene sulfide) resins are excellentpolymers having good thermal stability, chemical resistance, flameresistance, and electrical insulation properties. These physicalproperties make them useful as, for example, coatings for pipes, tanks,or pumps, in manufacturing extruded articles, films, sheets, or fibers,and in injection molded products for electronic or electricalapplications.

Generally, these polymers, when newly made, have a pleasant andattractive appearance due to extremely low coloration. They are,however, known to have a very high absorption of light in theultraviolet (hereinafter referred to as UV) region. Upon being exposedto solar or UV rays, these polymers darken in color. Furthermore,absorption of UV light may result in a decrease in some mechanicalproperties of the polymers.

The common method of stabilizing a polymer against light is by mixing itwith a protective agent. In comparison to coating finished products(films and fibers) with stabilizers or incorporation of photostabilizingfunctionalities into the polymer, the method based on bulk addition of aprotective agent is usually straightforward and can be technologicallysimple. To achieve optimal action without seriously affecting desiredproperties of a given polymer, a great deal of care, however, is calledfor in selecting the type and amount of a compatible additive useful asa protective agent.

Certain metals, metal compounds (including oxides, carbonates andsulfides), transition metal complexes, organotin azolides, pyrenederivatives, non-sulfur-containing hydroxyphenylbenzotriazolederivatives and special aniline-nitrobenzene dyes (nigrosins) have beenclaimed to improve UV stability of polymers and/or reduce radicalformation in polymers. For example, non-sulfur-containinghydroxyphenylbenzotriazole derivatives when added to a poly(arylenesulfide) polymer work well as stabilizers to reduce the deleteriouseffects of ultraviolet exposure upon the polymer. Unfortunately, thehigh melt processing temperatures of the polymer lead to loss of thesestabilizers through evaporation. The degree of UV light stabilizationafforded to the polymer by these known non-sulfur-containinghydroxyphenylbenzotriazole derivatives is thereby appreciably limited.

Therefore, it would be a significant contribution to the art if a newhydroxyphenylbenzotriazole derivative that is less volatile at thetemperatures used to process the polymers and affords a higher degree ofprotection against UV light can be developed.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a newhydroxyphenylbenzotriazole derivative that reduces the deleteriouseffect of UV light on a polymer. Another object of the invention is toprovide a process for synthesizing the hydroxyphenylbenzotriazolederivative. A further object of the invention is to provide a processfor synthesizing the hydroxyphenylbenzotriazole derivative in highyield. Yet another object of the invention is to provide ahydroxyphenylbenzotriazole derivative that is stable at the high meltprocessing temperatures of the polymers. Yet still another object of theinvention is to provide a hydroxyphenylbenzotriazole derivative that haslow volatility at the high melt processing temperatures of the polymers.Still a further object of the invention is to provide a process forstabilizing polymers against UV light absorption. Yet still a furtherobject is to provide a polymer composition that is UV stable and aprocess for producing the composition. Other objects, advantages andfeatures will become more apparent as the invention is more fullydisclosed hereinbelow.

According to a first embodiment of the present invention, a compositionthat, when present in a polymer matrix, reduces the deleterious effectof UV light absorption by the polymer is provided, which comprises asulfur-containing derivative of hydroxyphenylbenzotriazole having theformula of: ##STR2## wherein each X is a substituent selected from thegroup consisting of hydrogen, chlorine, bromine, iodine, fluorine,cyano, alkyl, phenyl group, biphenyl group, arylthio, amine, ketone,aldehyde, alkoxy, hydroxy, carboxylic acid group, oligomer andcombinations thereof; unless otherwise indicated, each X, if it is acarbon-containing substituent, can have carbon atoms from 1 to about 20;n is a whole number from 1 to 5; n' is a whole number from 0 to 4; n" isa whole number from 1 to 2 and each n" can be the same or different; qis an integer from 1 to 10; Y is selected from the group consisting of--S(O)(O)--, --S(O)--, and --S--; each R can be the same or differentand each can be selected from the group consisting of hydrogen, alkylgroup, alkenyl group, aralkyl group, alkaryl group, and combinationsthereof; when R has more than 2 carbon atoms, it can be linear,branched, or cyclic; each R, unless otherwise indicated, can have 0 toabout 10 carbon atoms; each OH group can be at either the 2'- or the6'-position, or both; and X, Y, and R can be at any available positionof the arylene rings.

According to a second embodiment of the invention a process forstabilizing a polymer against the deleterious effect of UV lightabsorption is provided which comprises contacting the polymer with asulfur-containing derivative of hydroxyphenylbenzotriazole having theformula of: ##STR3## wherein each X is a substituent selected from thegroup consisting of hydrogen, chlorine, bromine, iodine, fluorine,cyano, C₁ -C₂₀ alkyl, phenyl group, biphenyl group, arylthio, amine,ketone, aldehyde, C₁ -C₂₀ alkoxy, hydroxy, carboxylic acid group,oligomer and mixtures thereof; unless otherwise indicated, each X, if itis a carbon-containing constituent, can have carbon atoms from 1 toabout 20; n is a whole number from 1 to 5; n' is a whole number from 0to 4; n" is a whole number from 1 to 2 and each n" can be the same ordifferent; q is an integer from 1 to 10; each Y is selected from thegroup consisting of --S(O)(O)--, --S(O)--, --S--, and combinationsthereof; each R can be the same or different and each can be selectedfrom the group consisting of hydrogen, alkyl group, alkenyl group,aralkyl group alkaryl group, and combinations thereof; when R has morethan 2 carbon atoms, it can be linear, branched, or cyclic; each R,unless otherwise indicated, can have 0 to about 10 carbon atoms; each OHgroup can be at either the 2'- or the 6'-position, or both; and X, Y,and R can be at any available position of the arylene rings.

According to a third embodiment of the present invention, a process forsynthesizing a sulfur-containing derivative ofhydroxyphenylbenzotriazole having the formula of: ##STR4## is providedwhich comprises: (1) contacting a sulfur-containing aromatic compoundselected from the group consisting of thiophenolate anion andthiophenolic compound with a halo-substituted hydroxyphenylbenzotriazolederivative having the formula of: ##STR5## in the presence of a polarorganic compound to form an aryl sulfide derivative ofhydroxyphenylbenzotriazole; (2) contacting the aryl sulfide derivativeof hydroxyphenylbenzotriazole with an oxidizing agent to form either anaryl sulfoxide or an aryl sulfone derivative ofhydroxyphenylbenzotriazole, or mixture of aryl sulfoxide and arylsulfone derivatives of hydroxyphenylbenzotriazole; and (3) recoveringthe aryl sulfoxide derivative of hydroxyphenylbenzotriazole, the arylsulfone derivative of hydroxyphenylbenzotriazole, or the mixture of arylsulfoxide and aryl sulfone derivatives of hydroxyphenylbenzotriazole;wherein each X is a substituent selected from the group consisting ofhydrogen, chlorine, bromine, iodine, fluorine, cyano, alkyl, phenylgroup, biphenyl group, arylthio, amine, ketone, aldehyde, alkoxy,hydroxy, carboxylic acid group, oligomer, and combinations thereof;unless otherwise indicated, each X, if it is a carbon-containingconstituent, can have carbon atoms from 1 to about 20; n is a wholenumber of 1 to 5; n' is a whole number of 0 to 4; n" is a whole numberfrom 1 to 2 and each n" can be the same or different; q is an integer of1 to 10; each Y is selected from the group consisting of --S(O)(O)--,--S(O)--, --S--, and combinations thereof; each R can be the same ordifferent and each can be selected from the group consisting ofhydrogen, alkyl group, alkenyl group, an aralkyl group, an alkaryl groupand combinations thereof; when R has 2 or more carbon atoms, it can belinear, branched, or cyclic; each R, unless otherwise indicated, canhave 0 to about 10 carbon atoms; each X' is selected from the groupconsisting of chlorine, bromine, iodine, fluorine; each OH group can beat either the 2'- or the 6'-position, or both; and X, Y, R, and X' canbe at any available position of the arylene rings.

According to a fourth embodiment of the present invention, a UVlight-stable polymer composition is provided which comprises a polymerchemically bonded to a sulfur-containing derivative ofhydroxyphenylbenzotriazole where the composition has the formula of:##STR6## wherein each Z is a polymer; n is a whole number of 1 to 5; n'is a whole number of 0 to 4; n" is a whole number from 1 to 2 and eachn" can be the same or different; q is an integer of 1 to 10; each Y isselected from the group consisting of --S(O)(O)--, --S(O)--, --S--, andmixtures thereof; each R can be the same or different and each can beselected from the group consisting of hydrogen, alkyl group, alkenylgroup, an aralkyl group, an alkaryl group, and combinations thereof;when R has more than 2 carbon atoms, it can be linear, branched, orcyclic; each R, unless otherwise indicated can have 1 to 10 carbonatoms; each OH group can be at either the 2'- or the 6'-position, orboth; and Z, Y, and R can be at any available position of the arylenerings.

According to a fifth embodiment of the invention, a process is providedfor synthesizing a UV light-stable polymer composition where the polymeris chemically bonded to a sulfur-containing derivative ofhydroxyphenylbenzotriazole and the composition has the formula of:##STR7## wherein each Z is a polymer; n is a whole number of 1 to 5; n'is a whole number of 0 to 4; n" is a whole number from 1 to 2 and eachn" can be the same or different; q is an integer of 1 to 10; each Y isselected from the group consisting of --S(O)(O)--, --S--, and mixturesthereof; each R can be the same or different and are each selected fromthe group consisting of hydrogen, C₁ -C₁₀ alkyl group, C₂ -C₁₀ alkenylgroup, an aralkyl group, an alkaryl group, and combinations thereof;when R has more than 2 carbon atoms, it can be linear, branched, orcyclic; each R, unless otherwise indicated, can have 0 to about 10carbon atoms; each OH group can be at either the 2'-or the 6'-position,or both; and Z, Y, and R can be at any available position of the arylenerings; wherein the process comprises contacting a halo-substitutedsulfur-containing derivative of hydroxyphenylbenzotriazole with at leastone halogenated aromatic monomer and a sulfur source underpolymerization conditions to synthesize the polymer.

DETAILED DESCRIPTION OF INVENTION

According the first embodiment of the invention, a composition that,when present in a polymer matrix, reduces the effect of UV lightabsorption on a polymer comprises a sulfur-containing derivative ofhydroxyphenylbenzotriazole having the formula of: ##STR8## wherein eachX is a substituent selected from the group consisting of hydrogen,chlorine, bromine, iodine, fluorine, cyano, alkyl, phenyl group,biphenyl group, arylthio amine, ketone, aldehyde, alkoxy, hydroxy,carboxylic acid group, oligomer and mixtures thereof; unless otherwiseindicated, each X, if it is a carbon-containing substituent, can have 1to about 20 carbon atoms; n is a whole number of 1 to 5; n' is a wholenumber of 0 to 4; n" is a whole number from 1 to 2 and each n" can bethe same or different; q is an integer of 1 to 10; each Y is selectedfrom the group consisting of --S(O)(O)--, --S(O)--, --S--, andcombinations thereof; each R can be the same or different and each canbe selected from the group consisting of hydrogen, alkyl group, alkenylgroup, an aralkyl group, an alkaryl group, and combinations thereof;each R can have 0 to about 10 carbon atoms; when R has more than 2carbon atoms, it can be linear, branched, or cyclic; each OH group canbe at either the 2'- or the 6'-position, or both; and X, Y, and R can beat any available position of the arylene rings.

The term "oligomer" is used herein to refer to an organic moleculeconsisting of only a few monomer units, generally from 2 to about 10repeating units. Examples of oligomers are dimer, trimer, tetramer,octamer, and mixtures thereof. The term "polymer matrix" refers to acomposition comprising at least one polymer. The composition can be, forexample, a dry blend or melt blend.

Suitable sulfur-containing derivatives of hydroxyphenylbenzotriazole ofthe present invention include, but are not limited to,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(phenylthio)benzotriazole,2-(2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-aminophenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-aminophenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-aminophenylsulfonyl)benzotriazole,2-(3',5'-di-tert-cumyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole,2-(3',5'-di-tert-cumyl-2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-cumyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylsulfonyl)benzotriazole, and mixtures thereof.

The preparation of the sulfur-containing derivatives ofhydroxyphenylbenzotriazole of the present invention is describedhereinbelow in the third embodiment of the invention.

In the second embodiment of the present invention, a process forstabilizing a polymer against the deleterious effect of light,especially UV light absorption, is provided which comprises contactingthe polymer with a sulfur-containing derivative ofhydroxyphenylbenzotriazole. The scope of the sulfur-containingderivative of hydroxyphenylbenzotriazole is the same as that describedin the first embodiment of the invention.

The term "polymer" used herein refers to homopolymers, copolymers,terpolymers and tetrapolymers. It further refers to a high molecularweight organic compound whose structure can be represented by generallymore than about 10 repeating monomer units of simple molecules. Thepolymers can be synthesized by methods well-known in the art. Generally,the monomer units of the oligomer as described hereinabove in the firstembodiment of the invention are the same as those comprising the polymerto be stabilized.

The polymer suitable for the present invention can be any polymer thatis sensitive to UV light. Any physical forms of the polymer can bestabilized by the sulfur-containing derivatives ofhydroxyphenylbenzotriazole of the present invention. The physical formsinclude, but are not limited to pellets, powders, fibers, films, sheets,molded articles, and mixtures thereof. Examples of suitable polymersinclude, but are not limited to, poly(phenylene sulfide)s,poly(phenylene sulfone)s, poly(phenylene ether)s, poly(phenyleneketone)s, poly(phenylene ether ketone)s, poly(phenylene disulfide)s,poly(phenylene sulfide sulfone)s, poly(phenylene sulfide ketone)s,poly(phenylene sulfide disulfide)s, and copolymers thereof;polyethylene, polypropylene, poly(4-methyl-1-pentene), and copolymersthereof; polycarbonate; polyethylene terephthalate; and mixturesthereof.

The presently preferred polymer is a poly(phenylene sulfide) which iscommercially available from Phillips Petroleum Company, Bartlesville,Okla.

The process of the second embodiment of the invention can be carried outby a variety of means. The simplest means is to mix the polymer with thesulfur-containing derivative of hydroxyphenylbenzotriazole. Mixing canbe done by dry blending before melt processing, melt blending orsolvent-assisted methods. These mixing methods are well-known in theart.

The amount of a sulfur-containing derivative ofhydroxyphenylbenzotriazole required generally depends on the type ofpolymer and the desired degree of protection against ultraviolet light.A suitable amount is in the range of from about 0.01 to about 50 weight%, preferably from about 0.1 to about 20 weight %, and most preferablyfrom 0.5 to 15 weight % based on total weight of the final composition.

In the first step of the third embodiment of the invention, thesynthesis of the sulfur-containing derivative ofhydroxyphenylbenzotriazole of the first embodiment of the invention, ahalo-substituted hydroxyphenylbenzotriazole derivative having theformula of: ##STR9## is contacted with a sulfur-containing aromaticcompound in the presence of a polar organic compound at an elevatedtemperature; wherein each X' is a chlorine, bromine, iodine, fluorine ora suitable leaving group capable of being substituted by thesulfur-containing aromatic compound; n' is an integer from 0 to 4; n" isan integer from 1 to 2 and each n" can be the same or different; each Rcan be the same or different and each can be selected from the groupconsisting of hydrogen, alkyl group, alkenyl group, an aralkyl group, analkaryl group and mixtures thereof; each R can have 0 to about 10 carbonatoms; and when R has more than 2 carbon atoms, it can be linear,branched or cyclic; each OH group can be at the 2'- or the 6'-position,or both. Additionally, X' and R can be at any available position of thearylene rings. Examples of suitable halo-substitutedhydroxyphenylbenzotriazole derivatives include, but are not limited to,

2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,

2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-bromobenzotriazole,

2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-fluorobenzotriazole,

2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5,6-dichlorobenzotriazole,

2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5,6-dibromobenzotriazole,

2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5,6-difluorobenzotriazole,

2-(3',5'-di-n-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,

2-(3',5'-di-n-butyl-2'-hydroxyphenyl)-5-bromobenzotriazole,

2-(3',5'-di-n-butyl-2'-hydroxyphenyl)-5-fluorobenzotriazole,

2-(3',5'-di-i-propyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,

2-(3',5'-di-i-propyl-2'-hydroxyphenyl)-5-bromobenzotriazole,

2-(3',5'-di-i-propyl-2'-hydroxyphenyl)-5-fluorobenzotriazole,

2-(3',5'-di-i-propyl-2'-hydroxyphenyl)-5,6-dichlorobenzotriazole,

2-(3',5'-di-i-propyl-2'-hydroxyphenyl)-5,6-dibromobenzotriazole,

2-(3',5'-di-i-propyl-2'-hydroxyphenyl)-5,6-difluorobenzotriazole,

2-(3',5'-dimethyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,

2-(3',5'-dimethyl-2'-hydroxyphenyl)-5-bromobenzotriazole,

2-(3',5'-dimethyl-2'-hydroxyphenyl)-5-fluorobenzotriazole,

2-(3',5'-dimethyl-2'-hydroxyphenyl)-5,6-dichlorobenzotriazole,

2-(3',5'-dimethyl-2'-hydroxyphenyl)-5,6-dibromobenzotriazole,

2-(3',5'-dimethyl-2'-hydroxyphenyl)-5,6-difluorobenzotriazole,

2-(3',5'-dibenzyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,

2-(3',5'-dibenzyl-2'-hydroxyphenyl)-5-bromobenzotriazole,

2-(3',5'-dibenzyl-2'-hydroxyphenyl)-5-fluorobenzotriazole,

2-(3',5'-di-tert-butyl-2',6'-dihydroxyphenyl)-5-chlorobenzotriazole,

2-(3',5'-di-tert-butyl-2',6'-dihydroxyphenyl)-5-bromobenzotriazole,

2-(3',5'-di-tert-butyl-2',6'-dihydroxyphenyl)-5-fluorobenzotriazole,

and mixtures thereof. The presently preferred halo-substitutedhydroxyphenylbenzotriazole derivatives are2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-bromobenzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-fluorobenzotriazole, andmixtures thereof. The2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazolederivative is readily available from Ciba-Geigy under the tradename ofTinuvin 327.

The sulfur-containing aromatic compound suitable for the invention isselected from the group consisting of a thiophenolic compound having theformula of X_(n) --Ar--SH and a thiophenolate having the formula ofX_(n) --Ar--SM; the X substituent is selected from the group consistingof hydrogen, chlorine, bromine, iodine, fluorine, cyano, alkyl, alkenyl,phenyl group, biphenyl group, arylthio, amine, ketone, aldehyde,hydroxy, alkoxy, carboxylic acid group, oligomer, and combinationsthereof; each X, if it is a carbon-containing substituent, can have 1 toabout 20 carbon atoms; n is a whole number from 1 to 5; Ar is an arylenegroup; if n≧2, each X can be the same or different and can be at anyavailable position of the arylene ring; and M is an alkali metalselected from the group consisting of lithium, sodium, potassium,cesium, and mixtures thereof. Examples of the presently preferredsulfur-containing aromatic compound include, but are not limited to,thiophenol, sodium thiophenolate, 4-chlorothiophenol,3-chlorothiophenol, 4-bromothiophenol, 4-aminothiophenol,4-cyanothiophenol, 4-ethoxythiophenol, 4-hydroxythiophenol,2-aminothiophenol, 2-ethoxythiophenol, 2-methoxythiophenol, and mixturesthereof. The presently most preferred sulfur-containing aromaticcompound is thiophenol because of its ready availability.

The polar organic compound suitable for use in the present inventionwill generally substantially dissolve the reactants under the reactionconditions. Representative examples of suitable classes of the polarorganic compounds include amides, lactams, sulfones, and mixturesthereof. Specific examples of such polar organic compounds arehexamethylphosphoramide, tetramethylurea, N,N'-ethylene dipyrrolidone,N-methyl-2-pyrrolidone, pyrrolidone, caprolactam, N-ethylcaprolactam,sulfolane, dimethylacetamide, low molecular weight polyamides, andmixtures thereof. The presently most preferred polar organic compound isN-methyl-2-pyrrolidone because of its ease of use and readyavailability.

The process of the invention can also be carried out in the presence ofa basic compound and/or water. The basic compound used in the inventioncan be an organic base or an inorganic base and can be in either anaqueous or non-aqueous form. The presently preferred basic compound isan inorganic base. Examples of basic compounds include, but are notlimited to, tetramethylammonium hydroxide, potassium hydroxide, sodiumhydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide,ammonium hydroxide, lithium carbonate, sodium carbonate, potassiumcarbonate, calcium carbonate, magnesium carbonate, and mixtures thereof.The presently most preferred basic compounds are sodium hydroxide andsodium carbonate because of their availability and ease of use.

The molar ratio of the sulfur-containing aromatic compound to thehalo-substituted hydroxyphenylbenzotriazole derivative can vary fromabout 0.5:1 to about 4:1, preferably about 1:1 for amonohalo-substituted hydroxyphenylbenzotriazole derivative and about 2:1for a dihalo-substituted hydroxyphenylbenzotriazole derivative. Themolar ratio of the polar organic compound to the halo-substitutedhydroxyphenylbenzotriazole derivative is in the range of from about0.1:1 to about 100:1, preferably from 0.5:1 to 20:1. The molar ratio ofthe basic compound, if present, to the halo-substitutedhydroxyphenylbenzotriazole derivative is in the same range as that ofsulfur-containing aromatic compound to halo-substitutedhydroxyphenylbenzotriazole derivative. The molar ratio of water (ifpresent) to the halo-substituted benzotriazole derivative can be in therange of from about 0.0001:1 to about 20:1.

The aryl sulfide derivative of hydroxyphenylbenzotriazole synthesized bythe first step of the invention can be recovered for use as anultraviolet light stabilizer for polymers. It can also be used as astarting material for the synthesis of an aryl sulfoxide derivative ofhydroxyphenylbenzotriazole, an aryl sulfone derivative ofhydroxyphenylbenzotriazole, or mixtures of the aryl sulfoxidederivatives of hydroxyphenylbenzotriazole and aryl sulfone derivativesof hydroxyphenylbenzotriazole in the second step of the third embodimentof the invention.

In the second step of the third embodiment of the invention, the arylsulfide derivative of hydroxyphenylbenzotriazole is contacted with anoxidizing agent under conditions sufficient to oxidize an aryl sulfidederivative of hydroxyphenylbenzotriazole to an aryl sulfoxide derivativeof hydroxyphenylbenzotriazole, or an aryl sulfone derivative ofhydroxyphenylbenzotriazole, or mixtures thereof. A variation of reactionconditions such as, for example, reaction time, pressure and temperatureor oxidizing agents can be used to obtain different sulfur-containingderivatives of hydroxyphenylbenzotriazole.

Any oxidizing agent can be used in the oxidation of the aryl sulfidederivative of hydroxyphenylbenzotriazole. Suitable oxidizing agentsinclude, but are not limited to, hydrogen peroxide, peracetic acid,oxides of nitrogen, sodium peroxide, benzoyl peroxide, chlorine dioxide,m-chloroperbenzoic acid, m-bromoperbenzoic acid, p-chloroperbenzoicacid. In addition, an oxygen-containing fluid such as, for example,oxygen and air, also can be used in the second step of the thirdembodiment of the invention. The presently preferred oxidizing agentsare m-chloroperbenzoic acid and hydrogen peroxide because of their lowcost and availability.

Optionally, a catalyst can be employed to promote the oxidation.Suitable catalysts include, but are not limited to tungsten, molybdenum,vanadium, oxides thereof, and mixtures thereof. Specific examples ofsuitable catlaysts include, but are not limited to tungstic acid,vanadium oxide, vanadium(III) oxide, vanadium(V) oxide, tungsten(VI)oxide, tungsten, molybdenum, vanadium, and mixtures thereof.

The oxidation step also can be carried out in the presence of a solvent.The solvent, if employed, should be capable of substantiallysolubilizing the reactant and the oxidizing agent to improve thereaction. Examples of suitable solvents include, but are not limited to,tetrahydrofuran, carbon tetrachloride, methylene chloride, methanol,ethanol, isopropyl alcohol, propanol, and mixtures thereof. Thepresently preferred solvent is methylene chloride for it is easy torecover and recycle.

The molar ratio of the oxidizing agent to the aryl sulfide derivative ofhydroxyphenylbenzotriazole is in the range of from about 1:1 to about20:1, preferably from 1:1 to 10:1. The molar ratio of the solvent, ifpresent, to the aryl sulfide derivative of hydroxyphenylbenzotriazole isin the range of from about 10:1 to about 1000:1, preferably from 20:1 to200:1.

The process of synthesizing a sulfur-containing derivative ofhydroxyphenylbenzotriazole can be conducted in any suitable reactionvessel over a wide temperature range, pressure range and time range. Thechoice of a suitable reaction vessel is a matter of preference to oneskilled in the art. The selection of temperature, pressure, and timeranges for optimum results generally depends on the nature of thestarting material, the nature of desired products, the oxidizing agentemployed, and the solvent used. Broadly the temperature can be as low as5° C. and as high as 500° C. A preferred temperature in the first stepof the process is in the range of from about 100° C. to about 350° C.,most preferably 150° C. to 300° C. and that in the second step is in therange of from about 10° C. to about 150° C., most preferably from 15° C.to 90° C.

Broadly the operating pressure can be from slightly below atmospheric to300 atmospheres. It is however preferred the pressure be in the range offrom about 1 atmosphere to about 30 atmospheres, most preferably 1atmosphere to 15 atmospheres.

The time required for the synthesis of the sulfur-containing derivativeof hydroxyphenylbenzotriazole also can be varied from as short as atleast about 1 minute to as long as about 25 hours, preferably about 1minute to about 20 hours, most preferably 10 minutes to 15 hours foreach step of the third embodiment of the invention.

The sulfur-containing derivative of hydroxyphenylbenzotriazole can berecovered, if desired, from the reaction mixture by conventional meanssuch as solvent extraction, phase separation, crystallization followedby filtration, and other recovery means.

According to the fourth embodiment of the invention, a UV light-stablecomposition is provided which comprises a polymer chemically bonded to asulfur-containing derivative of hydroxyphenylbenzotriazole. The scopesof applicable polymers and sulfur-containing derivatives ofhydroxyphenylbenzotriazole are the same as those disclosed previously inthe second embodiment of the invention.

Examples of the presently preferred composition comprising a polymerchemically bonded to a sulfur-containing derivative ofhydroxyphenylbenzotriazole include, but are not limited to,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenylenesulfide)phenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenylenesulfide)phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenylenesulfide)phenylsulfonyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(2"-poly(phenylenesulfide)phenylthio)benzotriazole,2-(2'-hydroxyphenyl)-5-(2"-poly(phenylenesulfide)phenylsulfinyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(2"-poly(phenylenesulfide)phenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(3"-poly(phenylenesulfide)phenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(3"-poly(phenylenesulfide)phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(3"-poly(phenylenesulfide)phenylsulfonyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(4"-poly(phenylenesulfide)phenylthio)benzotriazole,2-(2'-hydroxyphenyl)-5-(4"-poly(phenylenesulfide)phenylsulfinyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(4"-poly(phenylenesulfide)phenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(3",4"-dipoly(phenylenesulfide)phenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(3",4"-dipoly(phenylenesulfide)phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(3",4"-dipoly(phenylenesulfide)phenylsulfonyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(2",4"-dipoly(phenylenesulfide)phenylthio)benzotriazole,2-(2'-hydroxyphenyl)-5-(2",4"-dipoly(phenylenesulfide)phenylsulfinyl)benzotriazole, 2-(2'-hydroxyphenyl)-5-(2",4"-poly(phenylenesulfide)phenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenylene sulfidesulfone)phenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenylene sulfidesulfone)phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenylene sulfidesulfone)phenylsulfonyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(2"-poly(phenylene sulfidesulfone)phenylthio)benzotriazole,2-(2'-hydroxyphenyl)-5-(2"-poly(phenylene sulfidesulfone)phenylsulfinyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(2"-poly(phenylene sulfidesulfone)phenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenyleneoxide)phenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenyleneoxide)phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenyleneoxide)phenylsulfonyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(2"-poly(phenyleneoxide)phenylthio)benzotriazole,2-(2'-hydroxyphenyl)-5-(2"-poly(phenyleneoxide)phenylsulfinyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(2"-poly(phenyleneoxide)phenylsulfonyl)benzotriazole, and mixtures thereof. The presentlymost preferred compositions are2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenylenesulfide)phenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenylenesulfide)phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-poly(phenylenesulfide)phenylsulfonyl)benzotriazole, and mixtures thereof.

The amount of sulfur-containing derivative of hydroxyphenylbenzotriazolethat is present in the composition is in the range of from about 0.0001to about 5 moles, preferably from about 0.001 to about 2 moles, and mostpreferably from 0.002 to 1.0 moles, per 100 repeat units of the polymer,or per gram-atom of sulfur which is present in sulfur-containingpolymers such as, for example, poly(arylene sulfide).

The preparation of the compositions of the fourth embodiment of theinvention is disclosed hereinbelow in the fifth embodiment of theinvention.

In the fifth embodiment of the invention, the composition disclosed inthe fourth embodiment of the invention is prepared by contacting ahalo-substituted sulfur-containing derivative ofhydroxyphenylbenzotriazole with a reaction mixture comprising a sulfursource and at least one halogen-containing aromatic monomer in a polarorganic compound under polymerization conditions to synthesize thepolymer. The term monomer is used herein, unless otherwise indicated, togenerically mean monomers, comonomers, termonomers, etc.

The halo-substituted sulfur-containing derivative ofhydroxyphenylbenzotriazole can be represented by the formula of:##STR10## wherein each X' is a chlorine, bromine, iodine, fluorine or asuitable leaving group capable of being substituted by thesulfur-containing aromatic compound; n is a whole number from 1 to 5; n'is an integer from 0 to 4; n" is an integer from 1 to 2 and each n" canbe the same or different; q is an integer of 1 to 10; and each Y isselected from the group consisting of --S(O)(O)--, --S--, andcombinations thereof; each R can be the same or different and each canbe selected from the group consisting of hydrogen, alkyl group, alkenylgroup, an aralkyl group, an alkaryl group and mixtures thereof; each Rcan have 0 to about 10 carbon atoms; and when R has more than 2 carbonatoms, it can be linear, branched or cyclic; each OH group can be at the2'- or the 6'-position, or both. Additionally, X', Y and R can be at anyavailable position of the arylene rings. The preferred halo-substitutedsulfur-containing derivative of hydroxyphenylbenzotriazole is selectedfrom the group consisting of2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-iodophenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-iodophenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-chlorophenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-chlorophenylsulfonyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(4"-bromophenylthio)benzotriazole,2-(2'-hydroxyphenyl)-5-(4"-bromophenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylsulfonyl)benzotriazole,and mixtures thereof. Other sulfur-containing derivatives ofhydroxyphenylbenzotriazole disclosed in the previous embodiments of theinvention can be reacted with a halogen in a solvent to prepare thesepreferred halo-substituted sulfur-containing derivatives ofhydroxyphenylbenzotriazole. The molar ratio of halogen to the othersulfur-containing derivatives of hydroxyphenylbenzotriazole is in therange of from about 0.1:1 to about 10:1, preferably from 0.5:1 to 2:1.Examples of the presently preferred solvent include, but are not limitedto, carbon tetrachloride, chloroform, methylene chloride,N-methyl-2-pyrrolidone, tetrahydrofuran, sulfolane, and mixturesthereof. The presently most preferred solvent is carbon tetrachloride.The molar ratio of the solvent to the other sulfur-containingderivatives of hydroxyphenylbenzotriazole can vary widely from about10:1 to about 5000:1, preferably from 50:1 to 1000:1. The reactionconditions can also vary widely, preferably in a temperature range offrom about -10° C. to about 80° C., preferably 0° C. to 50° C. for about1 hour to about 15 days under a pressure range of from about 1atmosphere to about 5 atmospheres, preferably about 1 atmosphere.

The presently preferred sulfur source is selected from the groupconsisting of alkali metal sulfides, alkali metal hydrosulfides,thiosulfates, thioureas, thioamides, and mixtures of any two or morethereof. Examples of the presently preferred sulfur source include, butare not limited to, sodium sulfide, sodium hydrosulfide, potassiumsulfide, potassium hydrosulfide, lithium thiosulfate, sodiumthiosulfate, potassium thiosulfate, rubidium thiosulfate,1-methyl-2-thiourea, 1,3-diisopropyl-2-thiourea, 1-p-tolyl-2-thiourea,thioacetamide, 2-thiopyrrolidone, and mixtures of any two or morethereof. The presently most preferred sulfur sources are sodium sulfideand sodium hydrosulfide because of availability and low cost.

The presently preferred halogen-containing aromatic monomer is ap-dihalobenzene having the formula of: ##STR11## where each X" isselected from the group consisting of fluorine chlorine, bromine, andiodine, and each R' is selected from the group consisting of hydrogenand hydrocarbyl radical in which the hydrocarbyl radical can be alkyl,cycloalkyl, and aryl radicals and combinations thereof such as, forexample alkaryl, and aralkyl, and the like, the total number of carbonatoms in each molecule being within the range of 6 to about 24.

Examples of some p-dihalobenzenes which can be employed in the processof this invention include p-dichlorobenzene, p-dibromobenzene,p-diiodobenzene, 1-chloro-4-bromobenzene, 1-chloro-4-iodobenzene,1-bromo-4-iodobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene,1-ethyl-4-isopropyl-2,5-dibromobenzene,1,2,4,5-tetramethyl-3,6-dichlorobenzene,1-butyl-4-cyclohexyl-2,5-dibromobenzene,1-hexyl-3-dodecyl-2,5-dichlorobenzene, 1-octadecyl-2,5-diiodobenzene,1-phenyl-2-chloro-5-bromobenzene, 1-p-tolyl-2,5-dibromobenzene,1-benzyl-2,5-dichlorobenzene,1-octyl-4-(3-methylcyclopentyl)-2,5-dichlorobenzene, and mixturesthereof.

The scope of the polar organic compound suitable for the fifthembodiment of the invention is the same as that for the third embodimentof the invention described above.

A basic compound also can be present in the polymerization reaction ofthe fifth embodiment of the invention. The scope of the basic compoundis the same as that disclosed for the third embodiment of the invention.

The process of the present invention can also be carried out bycontacting metal carboxylate with the reactants described above tomodify the molecular weight of the resulting copolymers. It can also becarried out in the presence of water. The metal carboxylate has theformula of R'CO₂ M where M is a metal selected from the group consistingof alkali metals and alkaline earth metals and R' is a hydrocarbylradical selected from the group consisting of alkyl, cycloalkyl, aryl,alkenyl, and mixtures of any two or more thereof. Preferably R' is analkyl radical having 1 to about 6 carbon atoms or a phenyl radical and Mis lithium or sodium. If desired, the metal carboxylate can be employedas a hydrate or as a solution or dispersion in water.

Examples of some metal carboxylates which can be employed in the processof this invention include, but are not limited to, lithium acetate,sodium acetate, potassium acetate, lithium propionate, sodiumpropionate, lithium 2-methylpropionate, rubidium butyrate, lithiumvalerate, sodium valerate, cesium hexanoate, lithium heptanoate, lithium2-methyloctanoate, potassium dodecanoate, rubidium4-ethyltetradecanoate, sodium octadecanoate, lithiumcyclohexanecarboxylate, cesium cyclododecanecarboxylate, sodium3-methylcyclopentanecarboxylate, potassium cyclohexylacetate, potassiumbenzoate, lithium benzoate, sodium benzoate, potassium m-toluate,lithium phenylacetate, sodium 4-phenylcyclohexanecarboxylate, potassiump-tolylacetate, lithium 4-ethylcyclohexylacetate, and mixtures of anytwo or more thereof.

According to the fifth embodiment of the present invention, thecontacting of the above described reactants can take place in thepresence of water. Water can also be formed from the interaction ofcertain sulfur sources and alkali metal hydroxides, if employed.

According to the fifth embodiment of the present invention, at least onehalogen-containing aromatic compound, a sulfur source, ahalo-substituted sulfur-containing derivative ofhydroxyphenylbenzotriazole, a polar organic compound, and optionallycompounds selected from the group consisting of a base, an alkali metalcarboxylate, a water source and mixtures thereof, are contacted in asuitable reactor to form a polymerization mixture. The choice of asuitable reactor is a matter of preference to one skilled in the art.The polymerization mixture then can be subjected to suitablepolymerization conditions. Suitable polymerization conditions can varywidely and generally include a temperature in the range of from about100° C. to about 400° C., preferably about 150° C. to about 350° C.,most preferably from 180° C. to 280° C., and a time of from about 5minutes to about 80 hours, preferably from about 10 minutes to about 70hours, most preferably from 1 hour to 30 hours. The pressure employed isnot critical, althought it is preferred that the pressure be sufficientto maintain the polymerization reactants substantially in the liquidphase.

The halo-substituted sulfur-containing derivative ofhydroxyphenylbenzotriazole may be present at the beginning of thepolymerization or may be added at any time during the polymerization.Alternatively, the polymerized resin may be treated with thehalo-substituted sulfur-containing derivative ofhydroxyphenylbenzotriazole and a sulfur source under suitablepolymerization conditions.

The molar ratio of reactants can vary considerably. However, the molarratio of the halogen-containing aromatic monomer to the sulfur source ispreferably from about 0.95:1 to about 1.20:1, most preferably from0.99:1 to 1.05:1 for best results.

If an alkali metal hydroxide is employed with a suitable sulfur source,the amount of alkali metal hydroxide to the sulfur source will varyaccording to the sulfur source but generally will be from about 0.001 toabout 5 and preferably 0.001 to 4 gram equivalents per gram-atom ofsulfur in the sulfur source.

If at least one alkali metal carboxylate is employed according to theinvention, the molar ratio of alkali metal carboxylate to the sulfursource is generally about 0.001:1 to about 1.5:1 and preferably about0.01:1 to about 1:1 to provide a polymer composition with desirablemolecular weight.

The amount of polar organic compound employed according to the inventioncan be expressed in terms of a molar ratio of polar organic compound tothe sulfur source. Generally, this ratio is about 2:1 to about 25:1 andpreferably about 2:1 to about 15:1 so that the reactants will besubstantially in a liquid state.

The process of the present invention can be conducted by various methodsincluding batch and continuous processes. One method is to admix thereactants described in a suitable reactor under the conditions describedabove.

The composition produced according to the present invention can beseparated from the final polymerization reaction mixture by conventionalprocedures, for example by filtration of the polymerization reactionmixture to separate the composition therefrom, followed by washing withwater. Alternatively, the heated polymerization reaction mixture can bediluted with water or additional polar organic compound or a mixturethereof followed by cooling and filtration and water washing of thepolymer. Preferably, at least a portion of the water washing isconducted at an elevated temperature, e.g. within the range of fromabout 30° C. to about 100° C., preferably from 50° C. to 95° C.

The polymer compositions produced by the process of the fifth embodimentof the invention can be blended with poly(phenylene sulfide)s, fillers,pigments, extenders, other polymers, and the like. They can be curedthrough crosslinking and/or chain extension by heating at temperaturesup to about 480° C., in the presence of a free oxygen-containing gas, toprovide cured products having high thermal stability and good chemicalresistance. They are useful in the production of coatings, film, moldedobjects, and fibers.

The following examples are provided to merely illustrate and are notintended to limit the scope of the present invention.

EXAMPLE I

This example illustrates the synthesis of2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole.

The run was carried out in a 300 ml autoclave equipped with a mechanicalstirrer and an overhead condensor. Thiophenol (11.55 g; 0.105 mol), 4.20g (0.105 mol) sodium hydroxide, 5.0 g (0.280 mol) water, and 90.0 g(0.908 mol) N-methyl-2-pyrrolidone (hereinafter referred to as NMP) wascharged to the 300 ml autoclave which was then sealed and purged with 50psi argon three times. Subsequent dehydration of the reaction mixturewas carried out by slowly increasing the autoclave temperature from 150°C. to 200° C. and allowing water to distill out through the condensor.Approximately 7.0 g of distillate was collected. The reaction mixturewas allowed to cool to 25° C., after which the autoclave top was removedand 35.97 g (0.10 mol)2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole (obtainedfrom Ciba-Geigy Corp.) and 60.0 g (0.605 mol) NMP was added. The reactorwas then resealed, repurged with argon, and heated to 200° C. for 6hours.

After cooling to 25° C., the heterogeneous reaction mixture (i.e., amixture of solvent and precipitated product) was worked up bytransferring the mixture from the autoclave with 200 ml of water andfurther diluting it (50/50 by volume) with a 50% aqueous solution ofHCl. The acidified mixture (pH=1) was extracted three times withmethylene chloride (400 ml). Recrystallization from the methylenechloride extract was achieved by first heating the extraction solvent toboiling followed by the slow addition of a 15% water/methanol solution(200 ml) until the solution retained a slight haze (occurs at about a50/50 dilution). The solution was then allowed to cool to 25° C. afterwhich it was placed in an ice bath (4° C.) for 2.5 hours. The resultingyellow, needle-like crystals were collected by suction filtration,washed with methanol (100 ml), and dried in a vacuum (25 torr) oven for3 hours at 100° C. The yield of this product was 32.93 g (76.2%). Thisproduct melts at 133° C. to 134° C. and is >99% pure by gaschromatography. Mass spectroscopy and carbon-13 NMR spectrometry of thisproduct showed it to be2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole.

EXAMPLE II

This example illustrates the synthesis of2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole.

The 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole(5.0 g; 0.012 mol) synthesized in Example I was dissolved in 50 g ofmethylene chloride in a 300 ml flask which was cooled on an ice bath at4° C. A magnetic stirring bar was used to mix the contents of the flask.With stirring, 8.2 g (2 equivalents of 50% reagent) ofm-chloroperbenzoic acid in 150 g methylene chloride was added slowlyover a period of about 30 minutes to the2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazolesolution under a nitrogen gas flow.

The reaction mixture was stirred under nitrogen for 3 hours at 25° C.Thereafter, precipitated solids were removed from the resulting reactionmixture by filtration. After an additional rinse of the solids withmethylene chloride, the solids were discarded. The filtrates werecombined, washed twice with a saturated solution of NaHCO₃ solution (100ml each wash), and subjected to rotary evaporation. The residue was thenrecrystallized from ethanol/H₂ O (volumetric ratio 80/20). The productwas recovered and dried as described in Example I. The product yield was4.87 g. Instrumental analyses (as described in Example I) showed it was2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole.

EXAMPLE III

This example illustrates the synthesis of a mixture of2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazoleand2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazoleby a catalytic oxidation of2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole.

The starting sulfide precursor2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenythio)benzotriazole(21.53 g) was stirred with 78.5 g of 2-propanol and 0.1 g of tungsticacid in a 300 ml 3-necked round-bottom flask under nitrogen. Thereaction mixture was then heated to 80° C. and 22.2 g of hydrogenperoxide was added slowly (over 1 hour).

The reaction was allowed to react at 80° C. for 12 hours. After thistime the reaction mixture was filtered. The filtered solid was washedwith 39.25 g of 2-propanol followed by 100 g of water and dried at 80°C. under vacuum (1 torr) for 24 hours. A yellow solid (19.18 g) wasrecovered after drying. Analysis of the product by GC showed it to be94.0 wt %2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole,4.6 wt %2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole,and 0.8 wt % unreacted2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole.

EXAMPLE IV

This example illustrates the manifestation of UV-inducedphotodegradation of poly(phenylene sulfide).

A. Poly(phenylene sulfide) (hereinafter referred to as PPS) iscommercially available from Phillips Petroleum Company, Bartlesville,Okla.

B. Film Preparation--PPS films were made directly from pellets, powder,or small chunks of the resin. A heat/press molding technique was usedfor preparing films. A weighed amount (2.7-3.0 g) of the resin (pellets,chunks, or powder) was placed between two 8"×8" Kapton sheets (2 mil)interspaced by a square frame, also made from a 2 mil Kapton sheet. Theinner open space of the frame was 7"×7", and was meant to be filled bythe resin in the course of melting and compression. The Kapton sheetswith the resin placed in between them were clamped together between twosteel plates and the resulting assembly was then placed in a hot pressmaintained at 320° C. With the clamping force maintained between1,000-2,000 pounds (16-32 psig) for 3 minutes, the resin was allowed tomelt and distribute itself in the space available between the Kaptonsheets. The clamping force was then raised to 35,000 pounds (550 psig)and maintained at that value for 3 minutes. Finally, the hot plate/sheetassembly was quickly removed from the hot press (following the releaseof the clamping force) and inserted between the platens of a cold press(maintained at 15°-20° C. by constant circulation of a cold tap waterthrough internal coils). The clamping force of the cold press was raisedto 35,000 pounds (550 psig) as soon as practicable and maintained therefor 2.5-3.0 minutes. This rapid cooling technique was suited to makingamorphous films.

In a few cases, the films ended up being predominantly crystalline inspite of rapid cooling. In such cases, amorphous films were obtained byquickly dipping the hot plate/sheet assembly in ice water baths. Thefilms prepared in this manner were characterized by slightly kinked(wavy) surfaces and tiny bubble-like blemishes in the bulk.

C. Irradiation Conditions--All of the photocoloration tests were done byuse of Xe-arc Weather-Ometers as irradiation sources. Two AtlasWeather-Ometers (models 600-W and Cl-35W) were used, but the bulk of thework was based on model 600-W. Both were equipped with high-pressure,5000 W, Xe lamps with borosilicate filters; the latter absorbed the deepUV portion of the lamp output and made available only the light in nearUV and visible regions. The intensities of the lamps were maintained at0.55 watt/m² (at 340 nm).

D. Color Change (ΔE) Measurements--A Hunter colorimeter, model D25OPTICAL SENSOR, was used in the reflection mode to determine filmcolors. Color values, as measured in a Hunter colorimeter whichsimulates the tristimulus response to human eyes, were resolved intothree components, namely, the lightness (L), green-to-red (a) andblue-to-yellow (b) scales. On the L-scale, the values of 100 and 0correspond to white and black, respectively (gray=50). On the a-scale, achange from negative to positive values means a change from green to red(gray=0), and a similar change on the b-scale denotes going from blue toyellow (gray=0). The overall color change (ΔE) experienced by a PPS filmupon UV exposure was calculated from the individual color values for thefilm before and after exposure using the following equation:

    ΔE=(ΔL.sup.2 +Δa.sup.2 +Δb.sup.2).sup.1/2

The color changes occurring upon UV exposure for films made from twocommercial fiber-grade PPS resins, PPS A and PPS B (both are availablefrom Phillips Petroleum Company, Bartlesville, Okla.), are shown inTable I.

                                      TABLE I                                     __________________________________________________________________________    Detailed Color Changes of Representative PPS Films                                           After 50 h Irradiation                                         Before Irradiation                                                                           in Weather-Ometer                                              Film L  a   b  L  a   b   L   a  b  E                                         __________________________________________________________________________    PPS A                                                                              84.09                                                                            -1.36                                                                             6.91                                                                             70.75                                                                             0.38                                                                             23.91                                                                             -13.34                                                                            1.74                                                                             17.00                                                                            21.7                                      PPS B                                                                              87.47                                                                            -1.38                                                                             5.24                                                                             75.33                                                                            -1.10                                                                             20.34                                                                             -12.14                                                                            0.28                                                                             15.10                                                                            19.4                                      __________________________________________________________________________

Table I shows that the color change for PPS B was slightly lower thanthat for PPS A. The major contributions to the overall color changes(ΔE) for both films came from a decrease of L (i.e., graying) and anincrease in b (i.e., yellowing). The changes in the a-scale wereinsignificant. It should also be noted that a ΔE value of less than 2 isimperceptible to the human eye.

Minor fluctuations in color change values were caused by lamp intensityvariations in the Weather-Ometers. For PPS films, color changes weretherefore normalized by comparisons to those of standard PPS filmsincluded as controls in every test. In order to avoid confusion thecommon practice was to include films as controls in every batch andnormalize the observed ΔE values of experimental films so that the ΔEfor the control was always about 20 units.

EXAMPLE V

This example shows that different post polymerization treatments andfilm preparation techniques had little or no effect on PPSphotodegradation behavior.

The tests for photodegradation were carried out the same as thosedescribed in Example IV.

Post-Polymerization Treatments--Films made from PPS resins that had beengiven the various treatments shown in Table II were exposed to UV lightas described in Example IV.C. The ΔE values given in Table II show nosignificant differences. The data in Table II demonstrate that theindicated post-polymerization treatments of PPS had little or no effecton photodegradation of PPS films.

                  TABLE II                                                        ______________________________________                                        Photocolorations of Treated Resin                                             Run         Wash.sup.a      ΔE                                          ______________________________________                                        1           Water           19.5                                              2           Water           20.5                                              3           Aqueous acetic acid                                                                           18.6                                              4           Aqueous calcium acetate                                                                       21.8                                              ______________________________________                                         .sup.a Resin (PPS A, Table I) was treated as shown after recovery from        polymerization mixture.                                                  

Film Thickness--Almost all of the photoinduced color change runs weredone with PPS films having thicknesses close to 2 mil. It was ofinterest to determine if the Hunter color parameters (L, a, b) for PPSfilms and their changes upon UV irradiation of the films were sensitiveto the film thicknesses. Table III shows data for films with thicknessesin the range of 2-6 mils. The ΔE's were essentially independent of filmthickness, in spite of the fact that the thickest film (6 mil) in thisset was a little darker (i.e., possessed a relatively low, initial Lvalue).

                                      TABLE III                                   __________________________________________________________________________    Effect of Film Thickness on Photocoloration of PPS A Films                                     After 50 h Irradiation                                       Thickness                                                                           Before Irradiation                                                                       in Weather-Ometer                                            (mil) L  a   b   L  a   b   ΔL                                                                          Δa                                                                           Δb                                                                         ΔE                              __________________________________________________________________________    2     83.34                                                                            -1.25                                                                             7.12                                                                              72.41                                                                            -0.82                                                                             23.77                                                                             -10.93                                                                            0.43 16.65                                                                            19.9                                  4     84.33                                                                            -1.07                                                                             9.37                                                                              72.29                                                                            -1.15                                                                             25.20                                                                             -12.04                                                                            -0.08                                                                              15.83                                                                            19.9                                  6     79.02                                                                            -1.25                                                                             10.11                                                                             68.33                                                                            -0.24                                                                             25.75                                                                             -10.69                                                                            1.01 15.64                                                                            19.0                                  __________________________________________________________________________

Resin Purification: Effect of Oligomer Content--The effect ofimpurities, especially cyclic and linear oligomers that are present tothe extent of 3-4 weight % in some commercial PPS resins onphotocoloration was also examined. A resin sample, from which theoligomers had been removed by exhaustive Soxhlet extraction withdichloromethane, was subjected to photostability tests followingredoping with varying amounts of the extracted oligomers. The UV-inducedcolor changes of the films are given in Table IV. Within experimentalerror, the oligomers, when added up to 20 wt. %, did not influence ΔE.The individual color components (i.e., L, a, and b parameters) weresimilarly unaffected.

Tables II to IV show that a variety of treatments of PPS resins did notproduce satisfactory results in stabilizing PPS polymers against UVdiscoloration.

                  TABLE IV                                                        ______________________________________                                        Effects of Oligomer Content on PPS Photocoloration                            Weight % of Extracted Oligomers Added                                         Back to Solvent-Extracted PPS                                                                         ΔE.sup.a                                        ______________________________________                                        0.0                     21.4 ± 0.9                                         0.50                    20.8 ± 1.0                                         1.25                    20.6 ± 1.5                                         2.5                     22.1 ± 0.4                                         5.0                     21.2 ± 1.5                                         10.0                    20.9 ± 1.3                                         20.0                    21.0 ± 0.5                                         ______________________________________                                         .sup.a After 50 hours irradiation in a WeatherOmeter.                    

EXAMPLE VI

This example illustrates the effect of sulfur-containing derivatives ofhydroxyphenylbenzotriazole of the invention on reducing thephotodegradation of PPS by UV irradiation.

PPS resin (3.0 g) was dry blended with sulfur-containing derivatives ofhydroxyphenylbenzotriazole in the amounts shown in Table V. Each blendwas mixed using a mortar and pestle and was then molded into a film asdescribed in Example IV. The films were used for the photodegradationtests described in Example IV, and the test data are shown in Table V.

                  TABLE V                                                         ______________________________________                                        UV-induced Color Changes of PPS Films Containing a                            Sulfur-Containing Derivative of Hydroxyphenylbenzotriazole                    Run No..sup.a                                                                              Additive     Wt. %   ΔE                                    ______________________________________                                        10           None         --      21.7                                        11           PTHPBT.sup.b 1.1     12.5                                        12           PTHPBT       1.9     11.4                                        13           PTHPBT       3.8     9.5                                         14           PTHPBT       4.6     7.6                                         15           PTHPBT       5.6     3.9                                         16           PTHPBT       7.6     4.7                                         17           PTHPBT       11.0    3.7                                         18           PTHPBT       7.9     5.1                                         19           PTHPBT       7.9     4.9                                         20           PSHPBT.sup.c 1.1     10.8                                        21           PSHPBT       2.5     8.4                                         22           PSHPBT       4.1     5.0                                         23           PSHPBT       6.1     2.7                                         24           PSHPBT       7.8     1.6                                         25           PSHPBT       11.3    1.0                                         ______________________________________                                         .sup.a The resin used for these runs was PPS A.                               .sup.b PTHPBT =                                                               2(3',5di-tert-butyl-2hydroxyphenyl)-5-(phenylthio)-benzotriazole.             .sup.c PSHPBT =                                                               2(3',5di-tert-butyl-2hydroxyphenyl)-5-(phenylsulfonyl)-benzotriazole.    

Data presented in Table V show that, with PSHPBT at 8-11% loadings, ΔE's<2 became achievable. Also Thermal Gravimetric Analysis (a test methodwhere a sample's weight loss is followed as its temperature isincreased) showed that both of the sulfur-containing derivatives ofhydroxyphenylbenzotriazole in Table V are nonvolatile at 310° C. andshould therefore be totally retained by the polymer during the hotcompression molding operation.

EXAMPLE VII

This example illustrates that the sulfur-containing derivatives ofhydroxyphenylbenzotriazole of the invention are also effectivephotostabilizers for PPS resins that had been treated with aqueoussolutions containing cations. The runs were carried out the same asthose in Example VI except that the resins were blended with the amountsof sulfur-containing derivatives shown in Table VI. The ΔE data given inTable VI show that at a comparable loading of the same UV-absorber, thecation-laced resins responded less favorably to the photostabilizingaction. For example, PPS films with 7.8-11.3 wt. % of PSHPBTconsistently gave ΔE's less than 2 (Table V), while PPS films producedfrom Ca⁺² -washed resins with PSHPBT in the same wt % range gave ΔE's inthe vicinity of 4 (Table VI). Washing of PPS is well-known to thoseskilled in the art.

                  TABLE VI                                                        ______________________________________                                        Effect of UV Stabilizers on Photostabilization                                of Cation-treated PPS Resins                                                  Run.sup.a    Additive (wt. %)                                                                           ΔE                                            ______________________________________                                        27           None         19.4                                                28           None         20.6                                                29           PSHPBT.sup.b (2.1)                                                                         9.2                                                 30           PSHPBT (4.0) 5.5                                                 31           PSHPBT (7.9) 3.7                                                 32           PSHPBT (11.9)                                                                              3.7                                                 33           PSHPBT (8.1) 4.2                                                 34           Tinuvin 327.sup.c (5.2)                                                                    5.1                                                 35           PSHPBT (8.1) 2.4                                                 36           Tinuvin 327 (4.9)                                                                          7.6                                                 37           PSHPBT (8.2) 4.8                                                 38           Tinuvin 327 (5.2)                                                                          6.6                                                 39           PTHPBT.sup.d (7.8)                                                                         7.4                                                 ______________________________________                                         .sup.a In run 27, the resin was not washed. In runs 28-34 and 39, the         resins were washed with aqueous Ca(OH).sub.2. In runs 37-38, the resin wa     washed with aqueous NaOH. In runs 35-36, the resins were washed with          aqueous Zn(OH).sub.2. All initial resins used in this Table were PPS B.       .sup.b See footnote c, Table V.                                               .sup.c Tinuvin 327 is a tradename for                                         2(3',5di-tert-butyl-2hydroxyphenyl)-5-chlorobenzotriazole which is            commercially available from CibaGeigy Corporation, Hawthorne, New York.       .sup.d See footnote b, Table V.                                          

EXAMPLE VIII

This example shows that the mixture of sulfur-containing derivatives ofhydroxyphenylbenzotriazole obtained in Example III can be used tostabilize PPS.

The runs were carried out the same as described in Example VI exceptthat the mixture of sulfur-containing derivatives ofhydroxyphenylbenzotriazole prepared in Example III was used as theadditive. The results are shown in Table VII.

                  TABLE VII                                                       ______________________________________                                        UV-induced Color Changes of PPS Films Containing a                            Mixture of Sulfur-containing Derivatives of                                   Hydroxyphenylbenzotriazole.sup.a                                              Wt % of Mixture of Sulfur-containing                                          Derivatives of Hydroxyphenylbenzotriazole                                     in PPS Films              ΔE.sup.b                                      ______________________________________                                        0                         20.0                                                2.1                       5.8                                                 4.0                       2.8                                                 5.9                       2.2                                                 8.1                       1.1                                                 10.4                      1.9                                                 ______________________________________                                         .sup.a See Example III.                                                       .sup.b After 50 hours of irradiation.                                    

As shown in Table VII, films made from the PPS resins containing themixture of sulfur-containing derivatives of the present invention hadmuch less color change as measured by ΔE after 50 hours of UVirradiation than did the unstabilized PPS films.

EXAMPLE IX

This example is a comparative example illustrating that mixing withcommercially available non-sulfur-containing hydroxyphenylbenzotriazolederivatives did not reduce the deleterious effect of UV on PPS aseffectively as the sulfur-containing hydroxyphenylbenzotriazolederivatives of the invention shown in Tables V and VII.

The runs were carried out the same as those described in Example VIexcept that the additives and concentrations thereof are as shown inTable VIII.

                  TABLE VIII                                                      ______________________________________                                        Effects of Commercial UV Stabilizers on PPS                                   Photostabilization                                                            Run.sup.a Additive     Weight %  ΔE.sup.a                               ______________________________________                                        22        PSHPBT.sup.b 4.1       5.0                                          40        Tinuvin 234.sup.c                                                                          1.0       9.7                                          41        Tinuvin 234  2.0       7.4                                          42        Tinuvin 234  3.0       8.1                                          43        Tinuvin 234  4.0       5.9                                          44        Tinuvin 327.sup.d                                                                          1.0       12.9                                         45        Tinuvin 327  2.1       9.2                                          46        Tinuvin 327  4.0       7.5                                          47        Tinuvin 328.sup.e                                                                          4.0       8.2                                          48        Cyasorb 531.sup.f                                                                          4.1       11.4                                         49        None         --        21.0                                         ______________________________________                                         .sup.a See footnote a, Table V.                                               .sup.b PSHPBT, see footnote c of Table V.                                     .sup.c Tinuvin 234 is a tradename for                                         2(3',5di-(α,dimethylbenzyl)-2hydroxyphenyl)benzotriazole                commercially available from CibaGeigy.                                        .sup.d See footnote c, Table VI.                                              .sup.e Tinuvin 328 is a tradename for                                         2(3',5di-tert-amyl-2hydroxyphenyl)benzotriazole commercially available        from CibaGeigy.                                                               .sup.f Cyasorb 531 is 2hydroxy-4-n-octyloxybenzophenone, commercially         available from American Cyanamid.                                        

Table VIII shows that films made from resins mixed with commerciallyavailable UV stabilizers at about 4% levels, though reducing the ΔEs,were not as effectively photostabilized as films containing theinventive additives (comparing runs 43, 47, and 48 with run 22). Forfurther comparison purposes, run 48, using a commercial UV stablizerthat is not a hydroxyphenylbenzotriazole derivative, was included toshow that it was not as effective for PPS photostabilization as theinventive stabilizers (compared to runs in Table V).

EXAMPLE X

This example demonstrates the synthesis of2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-bromophenylsulfonyl)benzotriazole.The starting sulfide precursor2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole(189.0 g) (Example I) was mixed with 1,195.5 g of carbon tetrachlorideunder argon. The mixture was then cooled with ice to about 0° C. for 1hour.

After this time a solution of 79.6 g bromine in 318.8 g carbontetrachloride was slowly added (over 65 min) to the cooled mixture.Following the addition of the bromine solution, the reaction mixture wasbrought to room temperature (25° C.) and stirred for 7 days.

The reaction product was worked up by removing the carbon tetrachloridevia rotary evaporation. The resulting solid was redissolved in carbontetrachloride (794.0 g), followed by removing the carbon tetrachloridevia rotary evaporation. The process was repeated in order to insure theremoval of all unreacted bromine. The resulting product wasrecrystallized from a 50/50 mixture of methylene chloride and awater-ethanol solution (15% water). The recrystallized product (yellowneedles) was collected and dried under vacuum (25 torr) at 127° C.overnight.

The dried product (197.17 g) had a melting point of 158°-159° C. and wasshown by GC to be >99% pure. Analysis of this product by massspectroscopy and NMR showed it to be2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-bromophenylthio)benzotriazole.

This product was further oxidized by the methods described in Example IIto make2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-bromophenylsulfonyl)benzotriazole.The identity of this product was confirmed by mass spectroscopy and NMRanalysis.

EXAMPLE XI

This example illustrates the synthesis of a polymer compositioncomprising poly(phenylene sulfide) which is chemically bonded to asulfur-containing derivative of hydroxyphenylbenzotriazole.

A 1-liter autoclave equipped with a mechanical stirrer and an overheadcondenser was charged with sodium hydrosulfide (95.33 g of 58.81% ofsolution; 1.0 mole), sodium hydroxide (41.57 g; 1.02 mole), NMP (250 g;2.5 moles) and sodium acetate (24.66 g; 0.3 mole). The autoclave wassealed up and purged three times with nitrogen (200 psi). The reactionmixture was heated with stirring (200 rpm) at a ramp rate of 3° C./minto 150° C. Dehydration was carried out from 150° C. to 208° C. byallowing water to distill out through the condensor. Approximately 39 mlof a distillate (97% water) was collected over the course of 45 minutes.At this point in the reaction, dichlorobenzene (DCB; 148.48 g; 1.01moles) in NMP (40.0 g; 0.40 moles) was charged to the reaction followedby an NMP (60.0 g; 0.60 moles) wash of the charging vessel.

The reaction mixture was then heated to 250° C. and held at 250° C. for120 minutes. The was followed by the addition of 5.89 g (0.01 mole) of2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-bromophenylsulfonyl)benzotriazole(synthesized as described in Example X) in 70 g (0.706 mole) of NMP tothe autoclave. The reaction mixture was held for an additional 30minutes at 250° C. (220 psig) and then cooled to 25° C.

The polymer product was collected on filter paper and washed twice with2 liters of acetone to remove any unreacted stabilizer. Theacetone-washed product was again washed twice with 2 liters of hot(about 100° C.) deionized water followed by drying in a vacuum oven (25torr) at 120° C. for 16 hours. A total of 103.0 g polymer was recovered.The polymer had an extrusion rate (measured at 315° C. by the method ofASTM D 1238-86, condition 315/0.345, modified to use an orfice having alength of 1.25 inches and a 5 minute preheat time) of 11.6 g/10 min. Afilm sample made from the product showed the presence of thehydroxyphenylbenzotriazole moiety when analyzed by UV spectroscopy.

EXAMPLE XII

This example illustrates that a poly(phenylene sulfide) that ischemically bonded to a sulfur-containing derivative ofhydroxyphenylbenzotriazole can also be made by adding thehalo-substituted sulfur-containing derivative ofhydroxyphenylbenzotriazole reagent at a different stage of thepolymerization process.

The condition of the run was identical to that described in Example XIexcept that2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-bromophenylsulfonyl)benzotriazolewas added to the autoclave before the reaction temperature reached 250°C. and the reaction mixture was held at 250° C. for 2 hours. The productwas worked up as described in Example XI. The recovered product weighed103.0 g.

The extrusion rate of this product was 108.9 g/10 minutes. A controlreaction run under these same conditions but without adding the2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-bromophenylsulfonyl)benzotriazoleproduced a product with an extrusion rate of 9.2 g/10 minutes.

Furthermore, a film sample made from a blend of the invention productwith PPS A showed the presence of the hydroxyphenylbenzotriazole moietywhen analyzed by UV spectroscopy.

EXAMPLE XIII

This example demonstrates that compositions comprising a poly(phenylenesulfide) polymer chemically bonded to a sulfur-containing derivative ofhydroxyphenylbenzotriazole (hereinafter referred to as PPS-S derivative)are resistant to UV-induced photodegradation.

Photodegradation tests of the inventive compositions were carried out bythe same procedure as described in Example IV using the polymer made inExample XI (run 51, Table IX). Table IX also shows the results ofphotodegradation of blends of 30% of PPS-S derivative and 70% PPS A (run52), of 50% PPS-S derivative and 50% PPS A (run 53), and of 75% PPS-Sderivative and 25% PPS A (run 54). The stabilizer concentrations in thefilms made from the three resin blends were estimated by UVspectrophotometry, and the estimates are reported in Table IX.Inhomogeneities in the blends cause deviations of measuredconcentrations from the expected values.

                  TABLE IX                                                        ______________________________________                                        Photodegradation of Poly(phenylene sulfide) Chemically                        Bonded To 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenyl-                 sulfonyl)benzotriazole                                                                       S-derivative                                                   Run            In Resin.sup.a                                                                           ΔE                                            ______________________________________                                        50             0          20.0                                                51             0.0020     8.9                                                 52             0.0004     11.0                                                53             0.0007     12.0                                                54             0.0017     8.4                                                 .sup. 55.sup.b 0.0030     12.9                                                .sup. 56.sup.b 0.0060     9.2                                                 ______________________________________                                         .sup.a The amount of UV stabilizer is expressed as moles of stabilizer pe     repeat unit of PPS polymer in the composition or in the blends (see text      for detail).                                                                  .sup.b In runs 55-56, the PPS polymers were made in the presence of           2(3',5di-tert-2hydroxyphenyl)-5-chlorobenzotriazole (a commercially           available product from CibaGeigy Corporation sold under the tradename of      Tinuvin 327) instead of the inventive                                         2(3',5di-tert-butyl-2hydroxyphenyl)-5-(4bromophenylsulfonyl)benzotriazole                                                                              

The results in Table IX indicated that chemically bonding as low as0.0004 mole (run 52) of the sulfur-containing derivative ofhydroxyphenylbenzotriazole per repeat unit of PPS resin resulted in asignificant reduction in ΔE. The ΔE further decreased to less than 9.0as the stabilizer content was increased to 0.0017 mole (run 54).Incorporation of a commercially available non-sulfur-containingderivative of hydroxyphenylbenzotriazole into PPS resins also decreasedthe ΔE (runs 55-56). However, for comparable reductions, considerablyhigher incorporation of the commercially available non-sulfur-containingderivative of hydroxyphenylbenzotriazole was required (runs 51-54compared with runs 55-56).

The results shown in the above examples clearly demonstrate that thepresent invention is well adapted to carry out the objects and attainthe ends and advantages mentioned as well as those inherent therein.While modifications may be made by those skilled in the art, suchmodifications are encompassed within the spirit of the present inventionas defined by the specification and the claims.

That which is claimed is:
 1. A composition comprising a poly(arylenesulfide) polymer and a sulfur-containing derivative ofhydroxyphenylbenzotriazole having the formula of: ##STR12## wherein saidsulfur-containing derivative of hydroxyphenylbenzotriazole is present insaid composition in an amount sufficient to impart UV ray protection tosaid poly(arylene sulfide); each X is a substituent selected from thegroup consisting of hydrogen, chlorine, bromine, iodine, fluorine,cyano, alkyl, phenyl group, biphenyl group, arylthio, amine, ketone,aldehyde, alkoxy, hydroxy, carboxylic acid group, and combinationsthereof; n is a whole number from 1 to 5; n' is a whole number from 0 to4; n" is a whole number from 1 to 2 and each n" can be the same ordifferent; q is an integer from 1 to 10; each Y is selected from thegroup consisting of --S(O)(O)--, --S(O)--, --S--, and combinationsthereof; each R can be the same or different and each is selected fromthe group consisting of hydrogen, alkyl group, alkenyl group, aralkylgroup, alkaryl group, and combinations thereof; at least one OH group isin an ortho position to the carbon bond to the triazine ring; and X, Y,and R can be at any available position of the arylene rings.
 2. Acomposition according to claim 1 wherein X is selected from the groupconsisting of hydrogen, chlorine, bromine, iodine, fluorine, andcombinations thereof.
 3. A composition according to claim 1 wherein saidsulfur-containing derivative of hydroxyphenylbenzotriazole is selectedfrom the group consisting of2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(phenylthio)benzotriazole,2-(2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-aminophenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-aminophenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-aminophenylsulfonyl)benzotriazole,2-(3',5'-di-tert-cumyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole,2-(3',5'-di-tert-cumyl-2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-cumyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylsulfonyl)benzotriazole,and mixtures thereof.
 4. A composition according to claim 1 wherein saidsulfur-containing derivative of hydroxyphenylbenzotriazole is2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole. 5.A composition according to claim 1 wherein said sulfur-containingderivative of hydroxyphenylbenzotriazole is2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole.6. A composition according to claim 1 wherein said sulfur-containingderivative of hydroxyphenylbenzotriazole is2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole.7. A composition according to claim 1 wherein said sulfur-containingderivative of hydroxyphenylbenzotriazole is2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-bromophenylthio)benzotriazole.8. A composition according to claim 1 wherein said sulfur-containingderivative of hydroxyphenylbenzotriazole is2-(3'-5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-bromophenylsulfonyl)benzotriazole.9. A composition according to claim 1 wherein said polymer ispoly(phenylene sulfide).
 10. A composition according to claim 1 whereinsaid polymer is mixed with said sulfur-containing derivative ofhydroxyphenylbenzotriazole.
 11. A composition according to claim 1wherein said sulfur-containing derivative of hydroxyphenylbenzotriazoleis present in said composition in the range of from about 0.01 to about50 weight % based on the combined total weight of said polymer and saidsulfur-containing derivative of hydroxyphenylbenzotriazole.
 12. Acomposition according to claim 1 wherein said sulfur-containingderivative of hydroxyphenylbenzotriazole is present in said compositionin the range of from 0.5 to 15 weight % based on the combined totalweight of said polymer and said sulfur-containing derivative ofhydroxyphenylbenzotriazole.
 13. A process for stabilizing a poly(arylenesulfide) polymer against the deleterious effect of light absorptioncomprising contacting said polymer with a sulfur-containing derivativeof hydroxyphenylbenzotriazole selected from the group consisting of2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(phenylthio)benzotriazole,2-(2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole,2-(2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-aminophenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-aminophenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-aminophenylsulfonyl)benzotriazole,2-(3',5'-di-tert-cumyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole,2-(3',5'-di-tert-cumyl-2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole,2-(3',5'-di-tert-cumyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylthio)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylsulfinyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxylphenyl)-5-(4"-bromophenylsulfonyl)benzotriazole,and mixtures thereof; wherein said sulfur-containing derivative ofhydroxyphenylbenzotriazole is present in an amount sufficient to impartUV ray protection to said polymer.
 14. A process according to claim 13wherein said sulfur-containing derivative of hydroxyphenylbenzotriazoleis 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylthio)benzotriazole.15. A process according to claim 13 wherein said sulfur-containingderivative of hydroxyphenylbenzotriazole is2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfinyl)benzotriazole.16. A process according to claim 13 wherein said sulfur-containingderivative of hydroxyphenylbenzotriazole is2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(phenylsulfonyl)benzotriazole.17. A process according to claim 13 wherein said sulfur-containingderivative of hydroxyphenylbenzotriazole is2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-bromophenylthio)benzotriazole.18. A process according to claim 13 wherein said sulfur-containingderivative of hydroxyphenylbenzotriazole is2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-(4"-bromophenylsulfonyl)benzotriazole.